Journal article

The INV24 test set: how well do quantum-chemical methods describe inversion and racemization barriers?

Lars Goerigk, Rahul Sharma

CANADIAN JOURNAL OF CHEMISTRY | CANADIAN SCIENCE PUBLISHING | Published : 2016

Abstract

For years, there has been ongoing interest in experimentally and theoretically understanding inversion and racemization processes. However, to the best of our knowledge, there has been no computational study that systematically investigated how well low-level quantum-chemical methods predict inversion barriers. Herein, we provide an answer to this question and we present the INV24 benchmark set of 24 high-level, ab initio inversion barriers. INV24 covers inversion in triatomics, in pyramidal molecules, in one cyclic system, and in various helical and bowl-shaped compounds. Our results indicate that previously applied DFT approximations combined with small basis sets are not reliable enough a..

View full abstract

University of Melbourne Researchers

Grants

Awarded by Australian Research Council Discovery Early Career Researcher Award


Funding Acknowledgements

We thank Asst/Prof. Amir Karton (The University of Western Australia) for helpful discussions on Wn-F12 theory and Dr. Andreas Hansen (University of Bonn) for support with the DLPNO-CCSD(T) calculations in the ORCA development version. L.G. is the recipient of an Australian Research Council Discovery Early Career Researcher Award (project No. DE140100550). L.G. also acknowledges funding from the Selby Scientific Foundation through the 2014 Selby Research Award as well as generous allocation of computing time from the National Computational Infrastructure (NCI) National Facility within the National Computational Merit Allocation Scheme.